CN1149304A - Fluorosilicone compound and composition containing the same - Google Patents
Fluorosilicone compound and composition containing the same Download PDFInfo
- Publication number
- CN1149304A CN1149304A CN95193303A CN95193303A CN1149304A CN 1149304 A CN1149304 A CN 1149304A CN 95193303 A CN95193303 A CN 95193303A CN 95193303 A CN95193303 A CN 95193303A CN 1149304 A CN1149304 A CN 1149304A
- Authority
- CN
- China
- Prior art keywords
- carbonatoms
- compound
- general formula
- agent
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 204
- 150000001875 compounds Chemical class 0.000 title claims abstract description 191
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 147
- 230000002940 repellent Effects 0.000 claims abstract description 37
- 239000005871 repellent Substances 0.000 claims abstract description 37
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 92
- -1 fluoro siloxane Chemical class 0.000 claims description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 125000001118 alkylidene group Chemical group 0.000 claims description 20
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 14
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000003921 oil Substances 0.000 abstract description 45
- 239000011248 coating agent Substances 0.000 abstract description 44
- 230000003373 anti-fouling effect Effects 0.000 abstract description 27
- 239000000565 sealant Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 60
- 239000003054 catalyst Substances 0.000 description 35
- 239000000654 additive Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000996 additive effect Effects 0.000 description 23
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 239000004519 grease Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229960001701 chloroform Drugs 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 150000005826 halohydrocarbons Chemical class 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- HZIFNFBYOMRJRX-UHFFFAOYSA-N 2-methyl-3-nonyloxirane Chemical compound CCCCCCCCCC1OC1C HZIFNFBYOMRJRX-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012230 colorless oil Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000003822 preparative gas chromatography Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 230000000683 nonmetastatic effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 101100256223 Caenorhabditis elegans cho-1 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010018612 Gonorrhoea Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical class [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
- B29C33/64—Silicone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
A novel fluorosilicone compound having at least two hydroxyl groups in the molecule, and a curable composition containing the compound and a general-purpose curing agent. The compound is suited for use in lubricant and fiber treatment, and the composition is suited for use in parting agent, water-and-oil repellent, antifouling coating agent, nontacky coating agent, optical coating agent, and sealant.
Description
Technical field
The present invention relates to a kind of new fluosilicic oxyalkane compound and solidified nature fluoro siloxane composition.And then relate to the lubricant that contains this fluosilicic oxyalkane compound or its composition, fiber with treatment agent, remover, water and oil repellent agent, didirtresistance apply agent, Abherent applies agent, optics with applying agent, sealing agent.
Background technology
Past all is because surface tension is lower as the known majority of solidification compound of principal constituent with siloxane polymer, therefore has performances such as water and oil-resistant, demoulding.Wherein, utilize the research of fluorosiloxane copolymer also to carry out in order further to improve the purpose of characteristics such as its water and oil-resistant, demoulding.
For example put down in writing a kind of containing in " シ リ コ-Application Ha Application De Block ッ Network " 559-592 page or leaf (Nikkan Kogyo Shimbun's distribution (1990))
Isostructural fluorosiloxane copolymer.Yet the performance of water-repellancy, grease proofness etc. that contains the solidification compound of these fluorosiloxane copolymers is good inadequately.And, be used to obtain the manufacturing process's complexity and the expense height of these fluorosiloxane copolymers.
In addition, for example open flat 5-301963 communique the spy, the spy opens and discloses the good solidified nature fluorosiloxane copolymer composition of a kind of water and oil-resistant in the flat 5-302034 communique, but this fluorosiloxane copolymer, if do not use special chlorine-containing compound as solidifying agent, then its intermiscibility is poor, solidify insufficiently, can not obtain satisfied performance.
On the other hand, state in the use under the situation of special solidifying agent, then too high as the cost of composition.
In addition, also having the people studying a kind of silane that contains perfluoroalkyl is that coupler adds in the solidified nature silicone composition to improve its water-repellancy, grease proofness, demoulding etc., but, or because its intermiscibility difference and can not obtain the cured film of homogeneous, perhaps, under the good situation of intermiscibility, its water-repellancy, grease proofness, demoulding etc. are good inadequately, therefore can not be satisfactory.
Existing solidified nature fluorosiloxane copolymer composition is owing to have above shortcoming, so its purposes is limited.
The objective of the invention is to provide a kind of solidified nature polysiloxane composition that can overcome above-mentioned shortcoming, just a kind ofly can use common solidifying agent, therefore cheap, and after curing, can form a kind of solidified nature fluorosiloxane copolymer composition, and be the new fluosilicic oxyalkane compound of host with it with cured film of low surface tension (high water-repellancy, high grease proofness, Abherent etc.).
Another purpose provides the various uses of the solidified nature fluorosiloxane copolymer composition that contains new fluosilicic oxyalkane compound.
Of the present invention open
That is to say, the present invention relates to a kind ofly with general formula (I) expression that have the fluosilicic oxyalkane compound (hereinafter referred to as fluosilicic oxyalkane compound (1)) of at least 2 hydroxyls in its molecule, said general formula (I) is:
(in the formula, R
fBe the perfluoroalkyl of carbonatoms 4～20, wherein the part of fluorine atom can replace by chlorine atom, hydrogen atom or by both; R
1Be the alkylidene group of carbonatoms 1～5 or the hydroxy alkylidene of carbonatoms 2～5; R
2Be the alkylidene group of carbonatoms 1～12, the oxyalkylene group of carbonatoms 2～50 or the hydroxy alkylidene of carbonatoms 3～15; R
3And R
4Can represent at least a in the fluoro-alkyl of alkyl, phenyl or carbonatoms 1～3 of carbonatoms 1～4 identical or differently; X is Sauerstoffatom, sulphur atom, NH or CO
2A is 5～1000 integer; But R
1Or R
2In to have one at least be above-mentioned hydroxy alkylidene).
In addition, the present invention relates to a kind of fluosilicic oxyalkane compound (hereinafter referred to as fluosilicic oxyalkane compound (II)) by general formula (II) expression, said general formula (II) is:
(in the formula, R
fBe the perfluoroalkyl of carbonatoms 4～20, wherein the part of fluorine atom can replace by chlorine atom, hydrogen atom or by both; R
1Be the alkylidene group of carbonatoms 1～5 or the hydroxy alkylidene of carbonatoms 2～5; R
2Be the alkylidene group of carbonatoms 1～12, the oxyalkylene group of carbonatoms 2～50 or the hydroxy alkylidene of carbonatoms 3～15; R
3, R
4, R
5And R
6Can represent at least a in the fluoro-alkyl of alkyl, phenyl or carbonatoms 1～3 of carbonatoms 1～4 identical or differently; X is Sauerstoffatom, sulphur atom, NH or CO
2Y and Z are integers, and its total amount is 5～1000 integer; Y/Z is 0.5～200 scope; But Z is more than 2, R
1Or R
2In to have one at least be above-mentioned hydroxy alkylidene).
In addition, the present invention relates to a kind of containing by more than a kind or 2 kinds and by the solidified nature fluoro siloxane composition more than a kind or 2 kinds of the compound of general formula (III) expression (hereinafter referred to as " solidified nature fluoro siloxane composition (I) ") of above-mentioned fluosilicic oxyalkane compound (I), said general formula (III) is:
(R
7)
aSiZ
4-a(III) (in the formula, R
7Be alkyl, fluoro-alkyl, alkenyl or phenyl; A is 0 or 1; Z be in halogen atom, alkoxyl group, acyloxy, ketoxime base, alkenyloxy, amino or the amide group more than a kind or 2 kinds).
In addition, the invention still further relates to a kind of more than a kind or 2 kinds and of above-mentioned fluosilicic oxyalkane compound (II) that contains by the solidified nature fluoro siloxane composition more than a kind or 2 kinds (hereinafter referred to as solidified nature fluoro siloxane composition (II)) of the compound of above-mentioned general formula (III) expression.
And, the invention still further relates to a kind of above-mentioned fluosilicic oxyalkane compound (I) or lubricant (II) and fiber treatment agent of containing.
Have again, the invention still further relates to a kind of above-mentioned solidified nature fluoro siloxane composition (I) or remover (II), water and oil repellent agent, didirtresistance coating agent, Abherent coating agent, the coating agent of optics usefulness and sealing agent of containing.
The preferred plan that is used to carry out an invention
Fluosilicic oxyalkane compound of the present invention (I) is represented by above-mentioned general formula (I).In said general formula (I), as R
f, for example be preferably: F-(CH
2)
b-(integers of b=4～20), (CF
3)
2CF-(CF
2)
c-(integers of c=2～16), H-(CH
2)
d-(integers of d=4～20) as its object lesson, can be enumerated: F-(CF
2)
6-, F (CF
2)
8-, F (CF
2)
10-, F (CF
2)
12-, F (CF
2)
14-, F (CF
2)
16-, F (CF
2)
18-, F (CF
2)
20-, (CF
3)
2CF-(CF
2)
2-, (CF
3)
2CF-(CF
2)
4-, (CF
3)
2CF-(CF
2)
6-, (CF
3)
2CF-(CF
2)
8-, (CF
3)
2CF-(CF
2)
10-, (CF
3)
2CF-(CF
2)
12-, (CF
3)
2CF-(CF
2)
14-, (CF
3)
2CF-(CF
2)
16-, H-(CF
2)
6-, H-(CF
2)
8-, H-(CF
2)
10-, H-(CF
2)
12-, H-(CF
2)
14-, H-(CF
2)
16-, H-(CF
2)
18-, H-(CF
2)
20-
As R
1, for example can enumerate :-(CH
2)
eThe alkylidene group of-(integers of e=1～5);
Deng hydroxy alkylidene.
As R
2, for example preferably :-(CH
2)
f-(integers of f=1～12) or contain
The divalent organic group of alkylidene groups such as (integers of g=1～5);
Oxyalkylene groups such as (h=0 or 1～15 integer, i=0 or 1～15 integer, the integers of j=1～10);
Deng hydroxy alkylidene,, can enumerate as its object lesson:
-CH
2CH
2OCH
2CH
2CH
2-
R
3And R
4Can be identical or different, as R
3Or R
4Preferred example, can enumerate: the alkyl of carbonatoms 1～4; Phenyl; The fluoro-alkyl of carbonatoms 1～3 as preferred concrete example, can be enumerated: alkyl such as methyl, ethyl, propyl group, butyl; CF
3CH
2CH
2-fluoro-alkyl of waiting etc.
As preferred X, can enumerate: Sauerstoffatom, sulphur atom ,-NH-or CO
2
A is 5～1000 integer, but considers from the performance of the low surface energy of water-repellancy, grease proofness, demoulding etc. and the viewpoints such as weather resistance of cured film, is preferably 10～500, is preferably 15～300 especially.
As the preferred concrete example of fluosilicic oxyalkane compound (I), can enumerate:
Fluosilicic oxyalkane compound of the present invention (II) is represented by above-mentioned general formula (II).In said general formula (II), as R
f, for example be preferably: F-(CH
2)
b-(integers of b=4～20), (CF
3)
2CF-(CF
2)
c-(integers of c=2～16), H-(CH
2)
d-(integers of d=4～20) as its object lesson, can be enumerated: F-(CF
2)
6-, F (CF
2)
8-, F (CF
2)
10-, F (CF
2)
12-, F (CF
2)
14-, F (CF
2)
16-, F (CF
2)
18-, F (CF
2)
20-, (CF
3)
2CF-(CF
2)
2-, (CF
3)
2CF-(CF
2)
4-, (CF
3)
2CF-(CF
2)
6-, (CF
3)
2CF-(CF
2)
8-, (CF
3)
2CF-(CF
2)
10-, (CF
3)
2CF-(CF
2)
12-, (CF
3)
2CF-(CF
2)
14-, (CF
3)
2CF-(CF
2)
16-, H-(CF
2)
6-, H-(CF
2)
8-, H-(CF
2)
10-, H-(CF
2)
12-, H-(CF
2)
14-, H-(CF
2)
16-, H-(CF
2)
18-, H-(CF
2)
20-
As R
1, for example can enumerate :-(CH
2)
eThe alkylidene group of-(integers of e=1～5);
Deng hydroxy alkylidene.
As R
2, for example preferably :-(CH
2)
f-(integers of f=1～12) or contain
The divalent organic group of alkylidene groups such as (integers of g=1～5);
Oxyalkylene groups such as (h=0 or 1～15 integer, i=0 or 1～15 integer, the integers of j=1～10);
Deng hydroxy alkylidene,, can enumerate as its object lesson:
-CH
2CH
2OCH
2CH
2CH
2-
R
3, R
4, R
5And R
6Can be identical or different.As preferred R
3, R
4, R
5And R
6, for example can enumerate: the alkyl of carbonatoms 1～4; Phenyl; The fluoro-alkyl of carbonatoms 1～3 as preferred concrete example, can be enumerated: alkyl such as methyl, ethyl, propyl group, butyl; CF
3CH
2CH
2-the fluoro-alkyl that waits.
Preferred X, can enumerate: Sauerstoffatom, sulphur atom ,-NH-or CO
2
Y and Z are integers, and their total amount is 5～1000 integer, is preferably 10～500 integer, and Y/Z is 0.5～200, is preferably 2～100 scope.But, when Z 2 when above, R
1And R
2In have at least one to be hydroxy alkylidene.
As the preferred concrete example of fluosilicic oxyalkane compound (II), can enumerate:
Fluosilicic oxyalkane compound (I) can be by for example making the compound and the compound of being represented by logical formula V by general formula (IV) expression, catalyzer exist or not in the presence of the method manufacturing of reacting,
Said general formula (IV) is:
(in the formula, R
2, R
3, R
4, X and definition (a) be the same)
Said logical formula V is:
(in the formula, R
fIdentical with above-mentioned definition, R
8For-CH
2-, CH
2OCH
2-,-CH
2CH
2OCH
2-)
As compound (IV), for example can enumerate:
As compound (V), for example can enumerate:
Fluorosilicone through compound (II) can by for example make by the compound of general formula (VI) expression and the compound of representing by logical formula V and in the presence of the catalyzer or the method for reacting not make, said general formula (VI) is:
(in the formula, R
2, R
3, R
4, R
5And R
6, X, Y and Z definition the same)
As compound (VI), for example can enumerate:
y+z1O0、y/z48
y+z150、y/z55
y+z120、y/z40
Y+z 150, y/z 50 etc.
In any reaction,, for example can use: BF as catalyzer
3Etherate, ZnCL
2, AlCl
3, SnCl
4Deng ammonium salts such as Lewis acid, trimethyl benzyl ammonia chloride etc.Temperature of reaction is 0～200 ℃, is preferably 40～150 ℃.Also can use reaction solvent.As reaction solvent, preferably do not hinder the solvent of each reacted constituent dissolving and reaction, for example can enumerate: CH
2Cl
2, CHCl
3, acetone, ethyl acetate, ether, toluene, chloro fluoroethane (HCFC-141b) etc.
In addition, also can be by making the have general formula silicone compounds of epoxy group(ing) shown in (VII) or silicone compounds with epoxy group(ing) shown in the general formula (VIII), react with compound shown in the general formula (IX) and to make above-mentioned fluosilicic oxyalkane compound (I) or (II)
Said general formula (VII) is:
(in the formula, A represents
R
9Expression C
1～C
12Alkylidene group, C
2～C
50Oxyalkylene group; R
3, R
4, a definition the same)
Said general formula (VIII) is:
(in the formula, R
3, R
4, R
5, R
6, R
9, A, Y, Z definition the same)
Said general formula (IX) is:
R
fR
10OH (IX) (in the formula, R
fDefinition the same, R
10The expression carbonatoms is 1～5 alkyl)
As compound (VII), for example can enumerate:
As compound (VIII), for example can enumerate:
As compound (IX), for example can enumerate: (CF
3)
2CF-(CF
2)
4-CH
2CH
2OH, (CF
3)
2CF-(CF
2)
6-CH
2CH
2OH, (CF
3)
2CF-(CF
2)
8-CH
2CH
2OH, (CF
3)
2CF-(CF
2)
10-CH
2CH
2OH, F-(CF
2)
6-CH
2CH
2OH, F-(CF
2)
8-CH
2CH
2OH, F-(CF
2)
10-CH
2CH
2OH, H-(CF
2)
4-CH
2OH, H-(CF
2)
6-CH
2OH, H-(CF
2)
8-CH
2OH, H-(CF
2)
10-CH
2OH
This reaction can according to (IV) or (VI) and the same condition of reaction (V) carry out.
Fluosilicic oxyalkane compound of the present invention (I) and (II) can perhaps cooperate with suitable additive or solvent individually is as lubricant or fiber treatment agent.
The invention still further relates to by fluosilicic oxyalkane compound (I) in addition or (II) and the solidified nature fluoro siloxane composition (I) that constitutes of the compound of above-mentioned general formula (III) expression or (II).
The compound of general formula (III) is a kind of solidifying agent, in general formula (III), as R
7, the alkyl of carbonatomss 1～20 such as methyl, ethyl, propyl group preferably; CF
3CH
2CH
2-, F-(CF
2)
2-CH
2CH
2-, F-(CF
2)
8CH
2CH
2-wait the fluoro-alkyl of carbonatoms 1～20; CH
2=CH-, CH
2=CHCH
2-wait the alkenyl of carbonatoms 2～5; Phenyl.Z is water-disintegrable residue, is preferably halogen atoms such as Cl, Br; CH
3O-, C
2H
5O-, (CH
3)
2The alkoxyl group of carbonatomss such as CHO-1～5, phenoxy group; CH
3COO-, CH
3CH
2The acyloxy of carbonatomss such as COO-2～5; (CH
3)
2C=N-O-,
Ketoxime base Deng carbonatoms 3～8:
Alkenyloxy Deng carbonatoms 3～15: CH
3NH-,
Deng amino: be preferably
Deng amide group.Consider preferred ketoxime base from aspects such as curing speed, package stability, raw material are easy to get.
As preferred compound (IH), for example can enumerate: CH
3Si (OCH
3)
3,
Fluosilicic oxyalkane compound of the present invention (I) and (II) can cooperate with various additives for example can be enumerated: electroconductibility imparting agent, weighting agent, tinting material, tackifier, thermo-stabilizer, UV light absorber etc.In addition, above-claimed cpd (I) and (II) can use separately, but also can be with for example aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halohydrocarbon, polysiloxane compound, ketone compound, the dilution of ester cpds equal solvent, the present invention is unqualified to this.
Above-mentioned fluosilicic oxyalkane compound (I) and (II) can perhaps cooperate individually with suitable additive or solvent, as all excellent lubrication agent such as oilness, solvent resistance, water-repellancy, grease proofness, flexibility etc. all fiber with excellent with treatment agent etc.
Solidified nature fluoro siloxane composition of the present invention (I) and (II) can cooperate with various additives, for example can enumerate: metal alkoxide classes such as metatitanic acid four alkane esters, germanic acid four alkane esters, zirconic acid four alkane esters, tri-alkoxy vanadium, the curing catalyst of organic acid salts such as zinc octoate, iron octoate, stannous octoate etc.; Carbon black, metals such as Ag, Cu, TiO
2Electroconductibility imparting agents such as quasi-metal oxides; Silicon-dioxide, mica, talcum, clay, diatomite, lime carbonate etc. are used to improve the weighting agent of hardness and intensity; Tinting material such as pigment, dyestuff; Tackifier such as silane coupling agent, titanic acid ester coupler; Thermo-stabilizers such as red iron oxide, titanium oxide, cerium oxide, barium zirconate; UV light absorber such as benzotriazole or benzophenone derivates etc.In addition, above-mentioned composition (I) and (II) can use separately, but also can use aliphatic hydrocarbons such as hexane, heptane, octane; Alicyclic hydrocarbon such as hexanaphthene; Aromatic hydrocarbon such as benzene,toluene,xylene; Methylene dichloride, trichloromethane, trichloroethane, Refrigerant R 113, dichloro one fluoroethane halohydrocarbon such as (HCFC-141b); Siloxane compound such as polysiloxane, cyclic polysiloxanes; Ketone compounds such as acetone, butanone, methyl iso-butyl ketone (MIBK); Ester compound such as ethyl acetate, butylacetate equal solvent dilution, perhaps form that also can mist is used, and the present invention is unqualified to this.
At above-mentioned solidified nature fluoro siloxane composition (I) with (II), fluosilicic oxyalkane compound (I) or (II) with the ratio that cooperates as the compound (HI) of solidifying agent, be 99/1～10/90 by weight, be preferably 98/2～30/70, if fluosilicic oxyalkane compound (I) or (II) very few, then cured film has the tendency of hardening, if too much, then cured film has the tendency of deliquescing.
Above-mentioned solidified nature fluoro siloxane composition (I) and (II) can be individually, perhaps cooperate with suitable additive or solvent, as solidified nature, for example remover, water and oil repellent agent, didirtresistance apply agent, Abherent applies agent, optics with applying uses such as agent or sealing agent.
The invention still further relates to a kind of by fluosilicic oxyalkane compound (I) and (II) individually, perhaps cooperate and the lubricant that constitutes with suitable additive or solvent.
The invention still further relates to a kind of by solidified nature fluoro siloxane composition (I) and (II) individually, perhaps cooperate and the remover that constitutes with suitable additive or solvent.
In the remover that constitutes by above-mentioned composition (I), as preferred fluosilicic oxyalkane compound (I), can enumerate by more than a kind or 2 kinds of the represented compound of general formula (I-e), particularly general formula (I-f),
Said general formula (I-e) is:
(in the formula, R
f, X, R
1, R
3, R
4, a definition the same; R
11Alkylidene group, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15 of expression carbonatoms 1～12)
Said general formula (I-f) is:
(in the formula, R '
fThe perfluoroalkyl of expression carbonatoms 6～20; X, R
1, R
3, R
4, a definition the same; R
11Alkylidene group, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15 of expression carbonatoms 1～12)
In the remover that constitutes by above-mentioned composition (II), as preferred fluosilicic oxyalkane compound (II), can enumerate by general formula (II-e), particularly the compound by general formula (II-f) expression is more than a kind or 2 kinds, said general formula (II-e) is:
(in the formula, R
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z definition the same)
Said general formula (I-f) is:
(in the formula, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z definition the same, R '
fExpression C
6～C
20Perfluoroalkyl)
By above-mentioned composition (I) or in the remover that (II) constitutes,, can enumerate above-mentioned compound as the compound of the general formula (III) of preferred consolidation agent.
As preferred concrete example in the above-mentioned general formula (I-e), can enumerate those in this (I-e), a is 10～500, R
fBe (CH
3)
2CF-(CF
2)
2～16Or F-(CF
2)
4～20, X is O or S, R
1For
, R
3, R
4Be methyl or ethyl, R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12Deng compound; As the preferred concrete example of above-mentioned general formula (I-f), can enumerate those in this (I-f), X, R
1, R
3, R
4, a definition the same, R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12, R '
fBe (CF
3)
2CF-(CF
2)
4～16Or F-(CF
2)
6～20Deng compound.
As the preferred concrete example of above-mentioned general formula (II-e), can enumerate those in this (II-e), R
f, X, R
1, R
3, R
4, R
11Definition the same, Y+Z=10～500, R
5, R
6=methyl, ethyl, the compound of Y/Z=2～100 grades; As the preferred concrete example of above-mentioned general formula (II-f), can enumerate those in this (II-f), R '
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, z the same compound of definition.
Preferred concrete example in the compound of above-mentioned general formula (III) can be enumerated above-mentioned compound.
At above-mentioned composition (I) or (II), above-mentioned fluosilicic oxyalkane compound (I) or (II) and the blending ratio of above-claimed cpd (III) be 99/1～20/80, be preferably 98/2～30/70, if this fluosilicic oxyalkane compound is very few, then cured film has the tendency of hardening, if this compound is too much, then cured film has the tendency of deliquescing.
Should illustrate, when above-mentioned silicon fluoride composition (I) with (II) when cooperating as metal alkoxide classes such as the metatitanic acid four alkane esters of curing catalyst or additives such as organic acid salt such as zinc octoate or stannous octoate, the blending ratio of this compound and additive is, with respect to above-mentioned fluosilicic oxyalkane compound (I) or (II) and 100 parts of (weight parts of the total amount of above-claimed cpd (III), as follows), this hardening accelerator is 0.2～20 part for example, is preferably 0.5～10 part.
If above-mentioned curing catalyst is few, then be solidified with slack-off tendency, if curing catalyst is too much, then demoulding has the tendency of variation.
In addition, above-mentioned fluoro siloxane composition (I) and (I) can use as remover individually, but also itself and for example aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halohydrocarbon, siloxane compound, ketone compound, the ester cpds equal solvent as thinner can be used, the blending ratio of this compound and solvent, with respect to 1 part of said composition, this thinner for example is 0.1500 part, preferred 1～200 part.
If above-mentioned thinner is very few, then there is viscosity to uprise, the tendency of cured film thickening if thinner is too much, then has viscosity, the tendency of cured film attenuation.
The remover that contains above-mentioned composition (I), persistence, the non-metastatic of its demoulding, demoulding are good, are suitable as remover and use.
The remover that contains above-mentioned composition (II), persistence, the non-metastatic of its demoulding, demoulding are good, are suitable as remover and use.
The invention still further relates to a kind of by solidified nature fluoro siloxane composition (I) and (II) individually, perhaps cooperate the water and oil repellent agent that forms with suitable additive or solvent.
As preferred fluosilicic oxyalkane compound (I) in the water and oil repellent agent of making by above-mentioned composition (I), can enumerate by general formula (I-g), particularly by in the compound of general formula (I-b) expression more than a kind or 2 kinds,
Said general formula (I-g) is:
(in the formula, R
f, X, R
1, R
2, R
3, R
4, a definition the same; R
11The expression carbonatoms is 1～12 alkylidene group, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15)
Said general formula (I-h) is:
(in the formula, R '
fThe perfluoroalkyl of expression carbonatoms 6～20; X, R
1, R
3, R
4, a definition the same; R
11Alkylidene group, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15 of expression carbonatoms 1～12)
As preferred fluosilicic oxyalkane compound (II) in the water and oil repellent agent of making by above-mentioned composition (II), can enumerate by general formula (II-g), particularly by in the compound of general formula (II-h) expression more than a kind or 2 kinds,
Said general formula (II-g) is:
(in the formula, R
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, z definition the same)
Said general formula (II-h) is:
(in the formula, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, z definition the same; R '
fExpression C
6～C
20Perfluoroalkyl)
In by above-mentioned composition (I) or the water and oil repellent agent (II) made,, can enumerate above-mentioned compound as the compound of the general formula (III) of preferred solidifying agent.
As the preferred concrete example of above-mentioned general formula (I-g), can enumerate those in this (I-g), a is 10～500, R
fBe (CH
3)
2CF-(CF
2)
2～16Or F-(CF
2)
4～20, X is O or S, R
1For
, R
3, R
4Be methyl or ethyl, R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12Deng compound; As the preferred concrete example of general formula (I-h), can enumerate those in this (I-h), R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12, R '
fBe (CF
3)
2CF-(CF
2)
4～16Or F-(CF
2)
6～20Deng compound.
As the preferred concrete example of above-mentioned general formula (II-g), can enumerate those in this (II-g), R
f, X, R
1, R
3, R
4, R
11Definition the same, Y+Z=10～500, R
5, R
6=methyl, ethyl, the compound of Y/Z=2～100 grades; As the preferred concrete example of above-mentioned general formula (II-h), can enumerate those in this (II-h), R '
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z the same compound of definition.
As the preferred concrete example of the compound of above-mentioned general formula (III), can enumerate those above-mentioned compounds.
In water and oil repellent agent of the present invention, above-mentioned fluosilicic oxyalkane compound (I) or (II) and the blending ratio of above-claimed cpd (III) be 99/1～20/80, be preferably 98/2～30/70, if this fluosilicic oxyalkane compound is very few, then cured film has the tendency of hardening, if this compound is too much, then cured film has the tendency of deliquescing.
Should illustrate, in water and oil repellent agent of the present invention, can cooperate metal alkoxide class or organic acid salt additives such as zinc octoate and stannous octoate such as metatitanic acid four alkane esters as curing catalyst, at this moment, the ratio of mixture of this compound and additive is, with respect to above-mentioned fluosilicic oxyalkane compound (I) or (II) and 100 parts of the total amounts of above-claimed cpd (III), this curing catalyst is 0.1～20 part for example, is preferably 0.2～10 part.
If the amount of above-mentioned curing catalyst is very few, then has and solidify slack-off tendency, if the amount of curing catalyst is too much.Then water and oil-resistant has the tendency of variation.
In addition, above-mentioned fluoro siloxane composition (I) and (II) can use as water and oil repellent agent individually, but, also can with its be used as aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halohydrocarbon, siloxane compound, ketone compound, the ester cpds equal solvent of thinner, the blending ratio of this compound and solvent, with respect to 1 part of said composition, for example this thinner is 0.1～500 part, is preferably 1～200 part.
If above-mentioned thinner is very few, then there is viscosity to uprise tendency with the cured film thickening, if thinner is too much, the tendency of viscosity and cured film attenuation is arranged then.
By the water and oil repellent agent that above-mentioned composition (I) is made, its water-repellancy, grease proofness are good, are suitable as water and oil repellent agent and use.
By the water and oil repellent agent that above-mentioned composition (II) is made, its water-repellancy, grease proofness are good, are suitable as water and oil repellent agent and use.
The invention still further relates to a kind of by solidified nature fluoro siloxane composition (I) and (II) individually, perhaps cooperate the didirtresistance that forms to apply agent with suitable additive or solvent.
Apply in the agent in the didirtresistance made by above-mentioned composition (I),, can enumerate by general formula (I-i) as preferred fluosilicic oxyalkane compound (I), particularly by in the compound of general formula (I-j) expression more than a kind or 2 kinds,
Said general formula (I-i) is:
(in the formula, R
f, X, R
1, R
2, R
3, R
4, a definition the same, R
11The expression carbonatoms is 1～12 alkylidene group, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15)
Said general formula (I-j) is:
(in the formula, R '
fThe expression carbonatoms is 6～20 perfluoroalkyl, X, R
1, R
3, R
4, a definition the same, R
11Alkylidene group, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15 of expression carbonatoms 1～12)
Apply in the agent in the didirtresistance made by above-mentioned composition (II),, can enumerate by general formula (II-i) as preferred fluosilicic oxyalkane compound (II), particularly by in the compound of general formula (II-j) expression more than a kind or 2 kinds,
Said general formula (II-i) is:
(in the formula, R
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z definition the same)
Said general formula (II-j) is:
(in the formula, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z definition the same; R '
fExpression C
6～C
20Perfluoroalkyl)
In by above-mentioned composition (I) or the water and oil repellent agent (I) made, as preferred solidifying agent, the compound of general formula (III) can be enumerated above-mentioned compound.
As the preferred concrete example of above-mentioned general formula (I-i), can enumerate those in this (I-i), a is 10～500, R
fBe (CH
3)
2CF-(CF
2)
2～16Or F-(CF
2)
4～20, X is O or S, R
1For
, R
3, R
4Be methyl or ethyl, R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12Deng compound; As the preferred concrete example of general formula (I-j), can enumerate those in this (I-j), R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12, R '
fBe (CF
3)
2CF-(CF
2)
4～16Or F-(CF
2)
6～20Deng compound.
As the preferred concrete example of above-mentioned general formula (II-i), can enumerate those in this (II-i), R
f, X, R
1, R
3, R
4, R
11Definition the same, Y+Z=10～500, R
5, R
6=methyl, ethyl, the compound of Y/Z=2～100 grades; As the preferred concrete example of above-mentioned general formula (II-j), can enumerate those in this (II-j), R '
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z the same compound of definition.
As the preferred example of the compound of above-mentioned general formula (III), can enumerate above-mentioned compound.
In antifouling coating agent of the present invention, above-mentioned fluosilicic oxyalkane compound (I) or (II) and the blending ratio of above-claimed cpd (III) be 99/1～20/80, be preferably 98/2～30/70, if this fluosilicic oxyalkane compound is very few, then cured film has the tendency of hardening, if this compound is too much, then cured film has the tendency of deliquescing.
Should illustrate, in antifouling coating agent of the present invention, can cooperate additives such as adding curing catalyst, tinting material, weighting agent, UV light absorber, electroconductibility imparting agent, the blending ratio of this compound and additive is, with respect to above-mentioned fluorosilane compounds (I) or (II) and 100 parts of the total amounts of above-claimed cpd (III), for example curing catalyst is 0.1～20 part, is preferably 0.2～10 part; UV light absorber is 0.1～10 part; The addition of weighting agent, tinting material, electroconductibility imparting agent can be selected in the scope of suitable width according to purposes.
The very few tendency that all has the effect of making to reduce of any amount in the above-mentioned additive, additive is crossed the tendency that has the didirtresistance of making to reduce at most.
In addition, above-mentioned fluoro siloxane composition (I) and (II) also can be used as antifouling coating agent individually and use, but also itself and for example aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halohydrocarbon, siloxane compound, ketone compound, the ester cpds equal solvent as thinner can be used, the blending ratio of this compound and solvent is, with respect to 1 part of said composition, for example this thinner is 0.1～500 part, is preferably 1～200 part.
If above-mentioned thinner is very few, then there is viscosity to uprise tendency with the cured film thickening, if thinner is too much, the tendency of viscosity and cured film attenuation is arranged then.
By the antifouling coating agent that above-mentioned composition (I) is made, its didirtresistance, water and oil-resistant are good, are suitable as antifouling coating agent and use.
By the antifouling coating agent that above-mentioned composition (II) is made, its didirtresistance, water and oil-resistant are good, are suitable as antifouling coating agent and use.
The invention still further relates to a kind of by solidified nature fluoro siloxane composition (I) and (II) individually, perhaps cooperate the Abherent that forms to apply agent with suitable additive or solvent.
Apply in the agent at the Abherent made by above-mentioned composition (I), as preferred fluosilicic oxyalkane compound (I), can enumerate in the compound of general formula (I-k), particularly general formula (I-l) more than a kind or 2 kinds,
Said general formula (I-k) is:
(in the formula, R
f, X, R
1, R
3, R
4, a definition the same, R
11The expression carbonatoms is 1～21 alkylidene group, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15)
Said general formula (II-1) is:
(in the formula, R '
fBe the perfluoroalkyl of carbonatoms 6～20, X, R
1, R
3, R
4, a definition the same, R
11Represent the alkylidene group of above-mentioned carbonatoms 1～12, the oxyalkylene group of carbonatoms 2～15 or the hydroxy alkylidene of carbonatoms 3～15).
Apply in the agent at the Abherent made by above-mentioned composition (II), as preferred fluosilicic oxyalkane compound (II), can enumerate in the compound of general formula (II-k), particularly general formula (II-1) more than a kind or 2 kinds,
Said general formula (II-k) is:
(in the formula, R
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z definition the same)
Said general formula (II-l) is:
(in the formula, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z definition the same, R '
fBe C
6～C
20Perfluoroalkyl)
In by above-mentioned composition (I) or the Abherent application composition (II) made, as preferred setting agent, the compound of general formula (III) can be enumerated above-mentioned compound.
As the preferred concrete example of above-mentioned general formula (I-k), can enumerate those in this (I-k), a is 10～500, R
fBe (CH
3)
2CF-(CF
2)
2～16Or F-(CF
2)
4～20, X is O or S, R
1For
, R
3, R
4Be methyl or ethyl, R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12Deng compound; As the preferred concrete example of general formula (I-l), can enumerate those in this (I-1), X, R
1, R
3, R
4, a is same as described above, R
11For-CH
2CH
2O-CH
2CH
2CH
2-or-(CH
2)
3～12, R '
fBe (CF
3)
2CF-(CF
2)
4～16Or F-(CF
2)
6～20Deng compound.
As the preferred concrete example of above-mentioned general formula (II-k), can enumerate those in this (II-k), R
f, X, R
1, R
3, R
4, R
11Definition the same, Y+Z=10～500, R
5, R
6=methyl, ethyl, the compound of Y/Z=2～100 grades; As the preferred concrete example of above-mentioned general formula (II-l), can enumerate those in this (II-l), R '
f, X, R
1, R
3, R
4, R
5, R
6, R
11, Y, Z the same compound of definition.
As the preferred concrete example of the compound of above-mentioned general formula (III), can enumerate above-mentioned compound.
Apply in the agent at Abherent of the present invention, above-mentioned fluosilicic oxyalkane compound (I) or (II) and the blending ratio of above-claimed cpd (III) be 99/1～20/80, be preferably 98/2～30/70, if this fluosilicic oxyalkane compound is very few, then cured film has the tendency of hardening, if this compound is too much, then cured film has the tendency of deliquescing.
Should illustrate that at above-mentioned fluoro siloxane composition (I) and (II), can cooperate additives such as adding curing catalyst, tinting material, weighting agent, UV light absorber, electroconductibility imparting agent, the ratio of mixture row of this compound and additive are.With respect to above-mentioned fluosilicic oxyalkane compound (I) or (II) and 100 parts of the total amounts of above-claimed cpd (III), for example curing catalyst is 0.1～20 part, be preferably 0.2～10 part, UV light absorber is 0.1～10 part, and the addition of weighting agent, tinting material, electroconductibility imparting agent can be selected in suitable scope according to purposes.
Any is very few in the above-mentioned additive, and its effect all has the tendency of reduction, if additive is too much, then Abherent has the tendency of reduction.
In addition, above-mentioned fluoro siloxane composition (I) and (II) also can apply agent individually and use as Abherent, but also itself and for example solvent as the aliphatic hydrocarbon of thinner, alicyclic hydrocarbon, aromatic hydrocarbon, halohydrocarbon, siloxane compound, ketone compound, ester cpds etc. can be used, the blending ratio of this compound and solvent is, with respect to 1 part of said composition, for example this thinner is 0.1～500 part, is preferably 1～200 part.
If above-mentioned thinner is very few, then there is viscosity to uprise tendency with the cured film thickening, if thinner is too much, the tendency of viscosity and cured film attenuation is arranged then.
The Abherent of being made by above-mentioned composition (I) applies agent, and its demoulding, Abherent are good, is suitable as Abherent and applies agent and use.
The Abherent of being made by above-mentioned composition (II) applies agent, and its demoulding, Abherent are good, is suitable as Abherent and applies agent and use.
The invention still further relates to a kind of by solidified nature fluoro siloxane composition (I) and (II) individually, perhaps cooperate the optics that forms with applying agent with suitable additive or solvent.
At the optics made by above-mentioned composition (I) with applying in the agent, as preferred fluosilicic oxyalkane compound (I), can enumerate in the compound of general formula (I-m), particularly general formula (I-n) more than a kind or 2 kinds,
Said general formula (I-m) is:
(in the formula, R
f, X, R
1, R
2, R
3, R
4Definition the same, b is 5～100 integer)
Said general formula (I-n) is:
(in the formula, R ' f is the perfluoroalkyl of carbonatoms 6～20, X, R
1, R
2, R
3, R
4, b definition the same)
With applying in the agent,, can enumerate the compound of general formula (II-m), particularly general formula (I-n) at the optics of making by above-mentioned composition (II) as preferred fluosilicic oxyalkane compound (II),
Said general formula (II-m) is:
(in the formula, Y+Z=5～100, Y/Z=0.5～100, other definition is the same)
Said general formula (II-n) is:
(in the formula, Y+Z=5～1000, Y/Z=0.5～100, R '
fBe the perfluoroalkyl of carbonatoms 6～20, other definition is the same)
By above-mentioned composition (I) or the optics (II) made with applying in the agent, as the preferred consolidation agent, the compound of general formula (III) can be enumerated above-mentioned compound.
As the preferred concrete example of above-mentioned general formula (I-m), can enumerate those in this (I-m), R
fFor
Or F-(CH
2)
4～20, X be O, S ,-NH-or-CO
2-, R
1For
, R
2Be CH
2CH
2OCH
2CH
2CH
2-or-(CH
2)
3～12, R
3, R
4Be CH
3, b is the compound of 5～100 integer; As the preferred concrete example of above-mentioned general formula (I-n), can enumerate those in this (I-n),
R '
f=(CH
3)
2CH-(CF
2)
4～16, F-(CF
2)
6～20, the compound that other definition is the same.
As the preferred concrete example of above-mentioned general formula (II-m), can enumerate those in this (II-m), R
fBe (CF
3)
2CF-(CF
2)
2～16Or F-(CF
2)
4～20, X be O, S ,-NH-or CO
2, R
1For
, R
2Be CH
2CH
2OCH
2CH
2CH
2-or-(CH
2)
3～12, R
3, R
4, R
5, R
6Be CH
3, Y+Z=5～1000, the compound of Y/Z=0.5～100; As the preferred concrete example of above-mentioned general formula (II-n), can enumerate those in this (II-n), R '
fBe (CF
3)
2CF-(CF
2)
4～16Or F-(CF
2)
6～20, the compound that other definition is the same.
As the preferred concrete example of the compound of above-mentioned general formula (III), can enumerate above-mentioned compound.
Use in the coating agent at optics of the present invention, above-mentioned fluosilicic oxyalkane compound (I) or (II) and the blending ratio of above-claimed cpd (III) be 99/1～20/80, be preferably 98/2～30/70, if this fluosilicic oxyalkane compound is very few, then the hardness of cured film and specific refractory power all have the tendency that uprises, if this compound is very few, then hardness and specific refractory power all have the tendency of reduction.
Should illustrate, use in the coating agent at optics of the present invention, can cooperate metal alkoxide class or the organic acid salt additives such as zinc octoate or stannous octoate of adding as metatitanic acid four alkane esters of solidified nature promotor etc., the blending ratio of this compound and additive is, with respect to above-mentioned fluosilicic oxyalkane compound (I) or (II) and 100 parts of the total amounts of above-claimed cpd (III), for example this curing catalyst is 0.1～20 part, is preferably 0.2～10 part.
If above-mentioned curing catalyst is very few, then be solidified with slack-off tendency, if curing catalyst is too much, then the transparency and storage stability have the tendency of reduction.
In addition, above-mentioned fluoro siloxane composition (I) and (II) also can use with applying agent individually as optics, but also itself and for example solvent as the aliphatic hydrocarbon of thinner, alicyclic hydrocarbon, aromatic hydrocarbon, halohydrocarbon, siloxane compound, ketone compound, ester cpds etc. can be used, this compound ratio is, with respect to 1 part of said composition, for example thinner is 0.1～500 part, is preferably 1～200 part.
If above-mentioned thinner is very few, then there is viscosity to uprise tendency with the cured film thickening, if thinner is too much, the tendency of viscosity and cured film attenuation is arranged then.
By the optics coating agent that above-mentioned composition (I) is made, its specific refractory power is low, and the transparency is good, is suitable as the coating agent use that optics is used.
The above-mentioned composition that contains above-claimed cpd (II), its specific refractory power is low, and the transparency is good, is suitable as the coating agent use that optics is used.
The invention still further relates to a kind of by solidified nature fluoro siloxane composition (I) and (II) individually, perhaps cooperate the sealing agent that forms with the additive or the solvent that are fit to.
In the sealing agent of making by above-mentioned composition (I), as preferred fluosilicic oxyalkane compound (I), can enumerate in the compound of general formula (I-o), particularly general formula (I-p) more than a kind or 2 kinds,
Said general formula (I-o) is:
(in the formula, R
f, X, R
1, R
2, R
3, R
4, a definition the same)
Said general formula (I-p) is:
(in the formula, R '
fBe the perfluoroalkyl of carbonatoms 6～20, X, R
1, R
2, R
3, R
4, a definition the same)
In the sealing agent of making by above-mentioned composition (H), as preferred fluosilicic oxyalkane compound (I), can enumerate in the compound of general formula (II-o), particularly general formula (II-p) more than a kind or 2 kinds,
Said general formula (II-o) is:
(in the formula, R
f, X, R
1, R
2, R
3, R
4, R
5, R
6, Y, Z definition the same)
Said general formula (II-p) is:
(in the formula, X, R
1, R
2, R
3, R
4, R
5, R
6, Y, Z definition the same, R '
fThe perfluoroalkyl of expression carbonatoms 6～20)
In by above-mentioned composition (I) or the sealing agent (II) made,, can enumerate above-mentioned compound as the compound of the general formula (III) of preferred consolidation agent.
As the preferred concrete example of above-mentioned general formula (I-o), can enumerate those in this (I-o), R
fFor
Or F-(CH
2)
4～20, X be O, S ,-NH-or-CO
2-, R
1For
, R
2Be CH
2CH
2OCH
2CH
2CH
2-or-(CH
2)
3～12, R
3, R
4Be CH
3, a is the compound of 5～1000 integer; As the preferred concrete example of above-mentioned general formula (I-p), can enumerate those in this (I-p), R
fBe (CH
3)
2CF-(CF
2)
4～16, F-(CF
2)
6～20, the compound that other definition is the same.
As the preferred concrete example of above-mentioned general formula (II-o), can enumerate those in this (II-o), R
fBe (CF
3)
2CF-(CF
2)
2～16Or F-(CF
2)
4～20, X be O, S ,-NH-or-CO
2-, R
1For
, R
2Be CH
2CH
2OCH
2CH
2CH
2-or-(CH
2)
3～12, R
3, R
4, R
5, R
6Be CH
3, Y+Z=5～1000, the compound of Y/Z=0.5～100; As the preferred concrete example of above-mentioned general formula (II-p), can enumerate those in this (II-p), R '
fBe (CF
3)
2CF-(CF
2)
4～16Or F-(CF
2)
6～20, the compound that other definition is the same.
As the preferred concrete example of the compound of above-mentioned general formula (III), can enumerate above-mentioned compound.
In sealing agent of the present invention, above-mentioned fluosilicic oxyalkane compound (I) or (II) and the blending ratio of above-claimed cpd (III) be 99/1～20/80, be preferably 98/2～30/70, if this fluosilicic oxyalkane compound is very few, then cured film has the tendency of hardening, if this compound is too much, then cured film has the tendency of deliquescing.
Should illustrate, in sealing agent of the present invention, can cooperate the additive that adds curing catalyst, tinting material, weighting agent, UV light absorber, electroconductibility imparting agent etc., the blending ratio of this compound and additive is, with respect to above-mentioned fluosilicic oxyalkane compound (I) or (II) and 100 parts of the total amounts of above-claimed cpd (III), for example curing catalyst is 0.1～20 part, be preferably 0.210 part, UV light absorber is 0.1～10 part, and the addition of weighting agent, tinting material, electroconductibility imparting agent can be selected in the scope of suitable width according to purposes.
Any of above-mentioned additive is very few, and its effect all has the tendency that reduces, if additive is too much, then solidified nature, water-repellancy, grease proofness, didirtresistance all have the tendency of reduction.
By the sealing agent that above-mentioned composition (I) is made, its solidified nature, stopping property, water-repellancy, grease proofness, didirtresistance are good, are suitable as sealing agent and use.
By the sealing agent that above-mentioned composition (II) is made, its solidified nature, stopping property, water-repellancy, grease proofness, didirtresistance are good, are suitable as sealing agent and use.
Specifically describe fluosilicic oxyalkane compound of the present invention and contain this compound compositions according to embodiment below, but the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
ジ system ロ-ト cooling tube, thermometer, nitrogen ingress pipe, dropping funnel are installed to one, internal volume is to add in 4 mouthfuls of flasks of 300ml
(mean value of n=22) (the シ リ of SHIN-ETSU HANTOTAI コ-Application (strain) system, trade(brand)name alcohol modified silicon oil (ァ Le コ-Le sex change シ リ コ-Application is the ィ Le) KF-6001) 40g adds trichloromethane 100ml, uses nitrogen replacement then.
Add BF
3Etherate 0.5ml, reflux, and meanwhile by dropping funnel drip at leisure the different nonyl propylene oxide of perfluor (
, 23.1g (44mm0l).Heated and stirred 18 hours after confirming that with vapor-phase chromatography this oxide compound disappears, successively with 1N-HCl, the washing of 10% sodium bicarbonate aqueous solution, is used MgSO
4Dry after-filtration under reduced pressure concentrates filtrate, obtains the colorless oil (yield 90%) of 57g.
To the product that is obtained among the embodiment 1, by
1H and
19The nuclear magnetic resonance absorption method of F (NMR) (analysis condition: resonant frequency is 300MHz for Block Le カ (strain) system, trade(brand)name AC-300 type, and base peak is,
1H: methyl-monosilane;
19F: fluoro trichloromethane; Solvent is CDCl
3), the data that obtained are shown below and the chemical structure of the product identified according to these data.
1HNMRδ0.01s(152H)i、δ0.55m(4H)h、δ163m(4H)g、δ4.25s(2H)j、δ3.3～3.8m(18H)b，c，d，e，f、
δ2.3?m(4H)a
19FNMR
-73ppm(6F)a、
-113.5ppm(2F)h、
-116ppm～-124.5ppm(10F)
c，d，e，f，g、
-187ppm(1F)b
Embodiment 2
Except using 20.9g's
Replace the 23.1g among the embodiment 1
Outward, all the other carry out similarly to Example 1, have obtained the colorless oil (yield 90%) of 54.6g.
To the product of embodiment 2, measure by NMR similarly to Example 1, the data that record are shown below and the chemical structure of the product identified according to these data.
1H NMR is identical with embodiment 1,
19FNMR
-81.4ppm(3F)a、-110.7～
-113.6ppm
(2F)h、-121.0ppm～-123.1ppm
(10F)c，d，e，f，g、-125.8ppm
(2F)b
Embodiment 3
ジ system ロ-ト cooling tube, thermometer, nitrogen ingress pipe, dropping funnel are installed to one, internal volume is to add in 4 mouthfuls of flasks of 100ml
(mean value of n=74) (the シ リ of SHIN-ETSU HANTOTAI コ-Application (strain) system, trade(brand)name alcohol modified silicon oil KF-6003) 25g adds trichloromethane 50ml, uses nitrogen replacement then.
Add BF
3Etherate 0.5ml, on one side reflux, on one side by the dropping funnel different nonyl propylene oxide of perfluor that drips at leisure
5.6g.Heated and stirred 18 hours after confirming that with vapor-phase chromatography this oxide compound disappears, washes with water, uses MgSO
4Dry after-filtration under reduced pressure concentrates filtrate, obtains the colorless oil (yield 96%) of 29.5g.
About the product of embodiment 3, measure by NMR similarly to Example 1, the data that record are shown below and the chemical structure of the product identified according to these data.
1HNMR
δ0.01s(458H)i、δ0.55m
(4H)h、
δ1.63m(4H)g、δ4.25s(2H)j、
δ3.3～3.8?m(18H)b，c，d，e，f、
δ2.3m(4H)a
19FNMR
-73ppm(6F)a、-113.5ppm
(2F)h、
-116ppm～-124.5ppm(10F)
c，d，e，f，g??、
-187ppm(1F)b
Embodiment 4
ジ system ロ-ト cooling tube, thermometer, nitrogen ingress pipe, dropping funnel are installed to one, internal volume is to add in 4 mouthfuls of flasks of 100ml
(m=15, k+n=30) (East レ ダ ゥ コ-ニ Application グ (strain) system, trade(brand)name alcohol modified silicon oil SF8427) 12.6g, use nitrogen replacement behind the adding trichloromethane 50ml.
Add BF
3Etherate 0.5ml, on one side reflux, on one side by the dropping funnel different nonyl propylene oxide of perfluor that drips at leisure
6.3g.Heated and stirred 4 hours after confirming that with vapor-phase chromatography this oxide compound disappears, washes with water, uses MgSO
4Dry after-filtration under reduced pressure concentrates filtrate, obtains the faint yellow oily thing (yield 96%) of 18.1g.
To the product of embodiment 4, measure by NMR similarly to Example 1, the data that record are shown below and the chemical structure of the product identified according to these data.
1HNMR
δ0.0s(103H)i、δ0.45m(4H)h、
δ1.52m(4H)g、δ3.3～3.7brs(130H)
b，c，d，e，f、δ2.3m(4H)a
19FNMR
-73ppm(6F)a、-113.5ppm
(2F)h、
-116ppm～-124.5ppm(10F)
c，d，e，f，g、
-187ppm(1F)b
Embodiment 5
ジ system ロ-ト cooling tube, thermometer, nitrogen ingress pipe, dropping funnel are installed to one, internal volume is to add perfluoroalkyl ethyl alcohol (CF in 4 mouthfuls of flasks of 200ml
3CF
2(CF
2CF
2)
nCH
2CH
2OH (n=3～7, the mean value of n=3.77)) 4.3g adds 50ml methylene dichloride and 50mlHCFC225, uses nitrogen replacement after dissolving fully.
Add BF
3Etherate 0.5ml, Yi Bian reflux, Yi Bian drip at leisure by dropping funnel
(East レ ダ ゥ コ-ニ Application グ (strain) system, the epoxide modified silicone oil SF8413 of trade(brand)name) methylene dichloride (50ml) solution (30.6g).Heated and stirred 4 hours after confirming that with chromatography fluorine-containing alcohol disappears, washes with water, uses MgSO
4Dry after-filtration under reduced pressure concentrates filtrate, obtains the oyster white oily matter (yield 90%) of 31.3g.
About the product of embodiment 5, measure by NMR similarly to Example 1, the data that record are shown below and the chemical structure of the product identified according to these data.
1HNMR
0.05s(332H)a、δ0.45?m
(2?H)b、
δ1.55m(2H)a、δ2.3m(2H)i、
δ3.2～3.m(9H)d,e,f,g,b
19FNMR
-82ppm(3F)a、-111～114ppm
(2F)e??、
-118～124ppm(13F)c，d、-126ppm
(2F)b
Embodiment 6
ジ system ロ-ト cooling tube, thermometer, nitrogen ingress pipe, dropping funnel are installed to one, internal volume is to add in 4 mouthfuls of flasks of 100ml
(East レ ダ ゥ コ-ニ Application グ (strain) system, the sulfhydryl modified silicone oil BY16-838A of trade(brand)name) 33g, use nitrogen replacement behind the adding trichloromethane 50ml.
Add BF
3Etherate, on one side reflux, on one side by the dropping funnel different nonyl propylene oxide of perfluor that drips at leisure
6.3g.Heated and stirred 1.5 hours after confirming that with vapor-phase chromatography this oxide compound disappears, washes with water, uses MgS0
4Dry after-filtration under reduced pressure concentrates filtrate, obtains the colorless oil of 38g.
To the product of embodiment 6, measure by NMR similarly to Example 1, the data that record are shown below and the chemical structure of the product identified according to these data.
1HNMR
δ0.01s(300H)a、δ0.65?m
(2H)b、
δ1.67m(2H)c、δ2.3m(2H)g、
δ2.4～2.6?m(4H)d，e、δ3.4～
3.6(1H)f
19FNMR
-73ppm(6F)a、-113.5ppm
(2F)h、
-116ppm～-125ppm(10F)
c，d，e，f，g，
-187ppm(1F)b
Embodiment 7
ジ system ロ-ト cooling tube, thermometer, nitrogen ingress pipe, dropping funnel are installed to one, internal volume is to add in 4 mouthfuls of flasks of 100ml
(East レ ダ ゥ コ-ニ Application グ (strain) system, the carboxy-modified silicone oil BY16-750 of trade(brand)name) 7g, use nitrogen replacement behind the adding trichloromethane 20ml.
Add BF
3Etherate 0.5ml, on one side reflux, on one side by the dropping funnel different nonyl propylene oxide of perfluor that drips at leisure
6.3g.Heated and stirred 4 hours after confirming that with vapor-phase chromatography this oxide compound disappears, washes with water, uses MgSO
4Dry after-filtration under reduced pressure concentrates filtrate, obtains the faint yellow oily thing of 10g (yield 75%).
To the product of embodiment 7, carry out NMR similarly to Example 1 and measure, the data that record are shown below and the chemical structure of this product of identifying according to these data.
1HNMR
δ0.01s(96H)h、δ0.55m
(4H)g、
δ1.3～1.5brs(32H)e，f、
δ2.3～2.4?m(8H)a，d、δ3.5m
(2H)b、
δ4.1m(4?H)c
19FNMR
-73ppm(6F)a、-113.5ppm
(2F)h、
-116ppm～-124.5ppm(10F)
c，d，e，f，g，
-187ppm(1F)b
Reference example 1
Except using
7.7g replace (the CF among the embodiment 1
3)
2 
23.1g outside, all the other carry out similarly to Example 1, obtain 43.9g colorless oil (yield 92%).
To the product of reference example 1, carry out NMR similarly to Example 1 and measure, the data that record are shown below and the chemical structure of this product of identifying according to these data.
1?HNMR
δ0.01s(152H)i、δ0.55m
(4H)h、
δ1.63m(4H)g、δ4.25s(2H)j、
δ3.3～3.8m(18H)b，c，d，e，f、
2.3m(4H)a
Embodiment 8
Will be as the compound that obtains by embodiment 1 of composition (A), as the solidifying agent of composition (B)
And mix according to the cooperation ratio shown in the table 1 respectively as the curing catalyst (stannous octoate) of composition (C), obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and Abherent and applied agent solidified nature fluoro siloxane composition.
Above-mentioned composition is brushed in the aluminum metal pattern of the aluminium sheet of a 7cm * 15cm and inside dimensions 6cm φ * 1cm,, be cured, obtained test film 150 ℃ of heating 20 minutes down.
The test film that is obtained is estimated according to following test method.The results are shown in the table 2.
Table 1
Table 2
| Contact angle | Specific refractory power | The transparency | Intermiscibility (solvent-laden composition | Appearance of film (solidified nature) | Demoulding power | The molding surface | |||
| ????H 2O | N-hexadecane | ||||||||
| Embodiment | ????8 | ????117 | ????71 | ????1.390 | Transparent | Mix equably | Well | ????A | ????A |
| ????9 | ????115 | ????69 | ????1.394 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????10 | ????116 | ????70 | ????1.393 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????11 | ????116 | ????71 | ????1.392 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????12 | ????115 | ????70 | ????1.392 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????13 | ????112 | ????69 | ????1.405 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????14 | ????115 | ????70 | ????1.392 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????15 | ????120 | ????72 | ????1.378 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????16 | ????117 | ????70 | ????1.393 | ????″ | ????″ | ????″ | ????A | ????A | |
| ????17 | ????117 | ????70 | ????1.393 | ????″ | ????″ | ????″ | ????A | ????A | |
Test according to following steps.
Contact angle determination: use contact angle meter (consonance interfacial chemistry (strain) system), carry out, measure 5 drops, get its mean value as contact angle according to sessile drop method.
Removability test (demoulding performance of remover): in the aluminum metal pattern that an inside dimensions is 6cm φ * 1cm, brush remover, this metal pattern was heated 20 minutes down so that said composition is solidified at 150 ℃, thereby form cured film in the inboard of metal pattern.
The urethane composition of following composition is fully stirred with stirrer, be injected into then in the said metal pattern.
サ ニ レ ッ Network ス FA 912
1)100 parts
19 parts of ethylene glycol
5 parts of R-11 Trichloromonofluoromethanes
0.9 part of DABCO
(1,4-diazabicyclo (2,2,2) octane
0.025 part of dibutyl tin laurate
ミ リ is ネ-ト MTL
2)104 parts
Annotate: 1) Sanyo changes into the polyol of (strain) system;
2) isocyanic ester of Japanese Port リ ゥ レ Application (strain) system.
At room temperature solidified 10 minutes, and after forming the urethane molding, stretched by the peg that in the preliminary shaping process, inserts in the urethane, measure its tensile strength (g/cm with a tensile testing machine (rate of extension 20mm/min)
2), by its demoulding performance of following benchmark evaluation.
A:100g/cm
2Below.
B:100g/cm
2More than, 200g/cm
2Below.
C:200g/cm
2More than, 300g/cm
2Below.
D:300g/cm
2More than.
Finishability test (surface finishing of molding); Urethane molding behind demoulding in the removability test by its surface finishing of visual observations, is estimated by benchmark shown in following.
A: the finishability on surface is good.
B: on part surface, see aperture.
C: all arrive aperture outwardly.
Embodiment 9
Will as the compound that obtains by embodiment 1 of (A) composition and as the solidifying agent of (B) composition (
) mix according to the ratio of cooperation shown in the table 1 respectively, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
The above-mentioned composition brushing in an aluminium sheet and aluminum metal pattern similarly to Example 8, is cured by condition of cure shown in the table 1 (temperature, time), has obtained test film.
Obtaining test film has been carried out test similarly to Example 8.The results are shown in the table 2.
Embodiment 10
The compound that will obtain as the embodiment 1 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 1 respectively as the curing catalyst (tetrabutyl titanate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is coated in the plate and metal pattern of aluminum according to similarly to Example 8 method, is cured, obtained test film by the condition of cure of table 1.Obtaining test film has been carried out test similarly to Example 8.The results are shown in the table 2.
Embodiment 11
The compound that will obtain as the embodiment 1 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 1 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured according to the condition of cure of table 1 similarly to Example 8, has obtained test film.The test film that is obtained is carried out similarly to Example 8 test.The results are shown in the table 2.
Embodiment 12
The compound that will obtain as the embodiment 1 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 1 respectively as curing catalyst (stannous octoate) and the solvent (prestox cyclosiloxane) of (C) composition, obtained the solidified nature fluoro siloxane composition that remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion coating agent are used.
Above-mentioned composition is solidified according to the condition of cure of table 1 similarly to Example 9, obtained test film.Obtaining test film is carried out similarly to Example 1 test.The results are shown in the table 2.
Embodiment 13
The compound that will obtain as the embodiment 1 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 1 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured according to the condition of cure of table 1 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 2.
Embodiment 14
The compound that will obtain, the solidifying agent (CH of conduct (B) composition as the embodiment 1 of (A) composition
3Si (OCH
3)
3) and mix according to the ratio of cooperation shown in the table 1 respectively as the curing catalyst (tetrabutyl titanate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is solidified according to the condition of cure of table 1 similarly to Example 8, obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 2.
Embodiment 15
The compound that will obtain, the solidifying agent (C of conduct (B) composition as the embodiment 1 of (A) composition
8F
17CH
2CH
2Si (OCH
3)
3) and mix according to the ratio of cooperation shown in the table 1 respectively as the curing catalyst (tetrabutyl titanate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 1 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 2.
Embodiment 16
The compound that will obtain as the embodiment 2 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 1 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 1 similarly to Example 8, has obtained test film.The test film that is obtained is carried out similarly to Example 8 test.The results are shown in the table 2.
Embodiment 17
The compound that will obtain as the embodiment 2 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 1 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 1 similarly to Example 8, has obtained test film.Obtaining test film has been carried out test similarly to Example 8.The results are shown in the table 2.
Comparative example 1
The compound that will obtain as the embodiment 1 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 3 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain remover of the present invention, water and oil repellent agent, antifouling coating agent and non-adhesion and applied the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 4.
Comparative example 2
The compound that will obtain as the embodiment 1 of (A) composition, the solidifying agent of conduct (B) composition (
) and mix according to the ratio of cooperation shown in the table 3 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion and apply the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film has been carried out test similarly to Example 8.The results are shown in the table 4.
Comparative example 3
Will be as (A) composition, have on endways the OH base polydimethylsiloxane (
), as the solidifying agent (CH of (B) composition
3Si (OCH
3)
3) and mix according to the ratio of cooperation shown in the table 3 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion and apply the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 4.
Comparative example 4
Will be as (A) composition, have on endways the OH base polydimethylsiloxane (
), as the solidifying agent (C of (B) composition
8F
17CH
2CH
2Si-(OCH
3)
3) and mix according to the ratio of cooperation shown in the table 3 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion and apply the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 1 test.The results are shown in the table 4.
Comparative example 5
Will be as (A) composition, have on endways the OH base polydimethylsiloxane (
), as the solidifying agent (C of (B) composition
8F
17CH
2CH
2Si-(OCH
3)
3) and mix according to the ratio of cooperation shown in the table 3 respectively as curing catalyst (stannous octoate) and the solvent (HCFC-225) of (C) composition, obtain the solidified nature fluoro siloxane composition that a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion coating agent are used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 4.
Comparative example 6
Will be as (A) composition, have on endways the OH base polydimethylsiloxane (
), as the solidifying agent (C of (B) composition
8F
17CH
2CH
2Si (OCH
3)
3) and mix according to the ratio of cooperation shown in the table 3 respectively as curing catalyst (stannous octoate) and the solvent (HCFC-225) of (C) composition, obtain the solidified nature fluoro siloxane composition that a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion coating agent are used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 4.
Comparative example 7
Will be as (A) composition, have on endways the OH base polydimethylsiloxane (
), as the solidifying agent (C of (B) composition
8F
17CH
2CH
2Si (OCH
3)
3And CH
3Si (OCH
3)
3) and mix according to the ratio of cooperation shown in the table 3 respectively as the curing catalyst (stannous octoate) of (C) composition, obtains the solidified nature fluoro siloxane composition that a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion coating agent are used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 4.
Comparative example 8
Will be as (A) composition, have on endways the OH base polydimethylsiloxane (
), as the solidifying agent (CF of (B) composition
3CH
2CH
2Si (OCH
3)
3) and mix according to the ratio of cooperation shown in the table 3 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion and apply the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 4.
Comparative example 9
The compound that will be obtained, the solidifying agent (CH of conduct (B) composition as the reference example 1 of (A) composition
3Si (OCH
3)
3) and mix according to the ratio of cooperation shown in the table 3 respectively as the curing catalyst (stannous octoate) of (C) composition, obtain a kind of remover, water and oil repellent agent, antifouling coating agent and non-adhesion and apply the solidified nature fluoro siloxane composition that agent is used.
Above-mentioned composition is cured by the condition of cure of table 3 similarly to Example 8, has obtained test film.Obtaining test film is carried out similarly to Example 8 test.The results are shown in the table 4.
Table 3
Table 4
| Contact angle | Specific refractory power | The transparency | Intermiscibility (solvent-laden composition | Appearance of film (solidified nature) | Demoulding power | The molding surface | |||
| ????H 2O | N-hexadecane | ||||||||
| Comparative example | ????1 | ????105 | ????72 | ????1.386 | Well | Homogeneous | Solidify insufficient | ????A | ????C |
| ????2 | ????102 | ????58 | ????1.425 | ????″ | Homogeneous | Well | ????B | ????A | |
| ????3 | ????96 | ????44 | ????1.418 | ????＂ | Homogeneous | Well | ????B | ????A | |
| ????4 | ????78 | ????64 | ?????-- | Gonorrhoea | Two separate | Solidify insufficient and inhomogeneous | ????B | ????C | |
| ????5 | ????78 | ????63 | ?????-- | ????″ | Homogeneous | ????″ | ????B | ????C | |
| ????6 | ????85 | ????68 | ?????-- | ????″ | Homogeneous | ????″ | ????B | ????C | |
| ????7 | ????93 | ????55 | ?????-- | ????″ | Two separate | ????″ | ????B | ????C | |
| ????8 | ????106 | ????60 | ?????-- | Well | Homogeneous | Well | ????B | ????A | |
| ????9 | ????98 | ????52 | ????1.415 | ????″ | ????″ | ????″ | ????B | ????B | |
The possibility of industrial utilization
A kind of new fluosilicic oxyalkane compound is provided, can have obtained a kind of new solidification compound good with intermiscibility Common Curing Agents by this compound.
In addition, above-claimed cpd can be used for lubricant and fiber with in the inorganic agent, and the composition that contains the curing of above-claimed cpd and above-mentioned Common Curing Agents is suitable for using with coating agent and sealant as remover, water and oil repellent agent, soil resistance coating agent, Abherent coating agent, optics.
Claims (12)
1. one kind by general formula (I) expression, has the fluosilicic oxyalkane compound of at least 2 hydroxyls in its molecule, and said general formula (I) is:
(in the formula, R
fBe the perfluoroalkyl of carbonatoms 4～20, wherein the part of fluorine atom can replace by chlorine atom, hydrogen atom or by both; R
1Be the alkylidene group of carbonatoms 1～5 or the hydroxy alkylidene of carbonatoms 2～5; R
2Be the alkylidene group of carbonatoms 1～12, the oxyalkylene group of carbonatoms 2～50 or the hydroxy alkylidene of carbonatoms 3～15; R
3And R
4Can represent at least a in the fluoro-alkyl of alkyl, phenyl or carbonatoms 1～3 of carbonatoms 1～4 identical or differently; X is Sauerstoffatom, sulphur atom, NH or CO
2A is 5～1000 integer; But R
1Or R
2In to have one at least be above-mentioned hydroxy alkylidene).
2. fluosilicic oxyalkane compound by general formula (I) expression, said general formula I I is:
(in the formula, R
fBe the perfluoroalkyl of carbonatoms 4～20, wherein the part of fluorine atom can replace by chlorine atom, hydrogen atom or by both; R
1Be the alkylidene group of carbonatoms 1～5 or the hydroxy alkylidene of carbonatoms 2～5; R
2Be the alkylidene group of carbonatoms 1～12, the oxyalkylene group of carbonatoms 2～50 or the hydroxy alkylidene of carbonatoms 3～15; R
3, R
4, R
5And R
6Can represent at least a in the fluoro-alkyl of alkyl, phenyl or carbonatoms 1～3 of carbonatoms 1～4 identical or differently; X is Sauerstoffatom, sulphur atom, NH or CO
2Y and Z are integers, and its total amount is 5～1000 integer; Y/Z is 0.5～200 scope; But Z is more than 2, R
1Or R
2In to have one at least be above-mentioned hydroxy alkylidene).
3. one kind contains by general formula (I) expression, in its molecule, have in the fluosilicic oxyalkane compound of at least 2 hydroxyls more than a kind or 2 kinds with by the solidified nature fluoro siloxane composition more than a kind or 2 kinds in the compound of general formula (III) expression,
(in the formula, R
fBe the perfluoroalkyl of carbonatoms 4～20, wherein the part of fluorine atom can replace by chlorine atom, hydrogen atom or by both; R
1Be the alkylidene group of carbonatoms 1～5 or the hydroxy alkylidene of carbonatoms 2～5; R
2Be the alkylidene group of carbonatoms 1～12, the oxyalkylene group of carbonatoms 2～50 or the hydroxy alkylidene of carbonatoms 3～15; R
3And R
4Can represent at least a in the fluoro-alkyl of alkyl, phenyl or carbonatoms 1～3 of carbonatoms 1～4 identical or differently; X is Sauerstoffatom, sulphur atom, NH or CO
2A is 5～1000 integer; But R
1Or R
2In to have one at least be above-mentioned hydroxy alkylidene),
Said general formula (III) is:
(R
7)
aSiZ
4-a(III) (in the formula, R
7Be alkyl, fluoro-alkyl, alkenyl or phenyl; A is 0 or 1; Z be in halogen atom, alkoxyl group, acyloxy, ketoxime base, alkenyloxy, amino or the amide group more than a kind or 2 kinds).
4. one kind contains by general formula (II) expression, in its molecule, have in the fluosilicic oxyalkane compound of at least 2 hydroxyls more than a kind or 2 kinds with the compound of general formula (III) expression in the solidified nature fluoro siloxane composition more than a kind or 2 kinds, said general formula (II) is:
(in the formula, R
fBe the perfluoroalkyl of carbonatoms 4～20, wherein the part of fluorine atom can replace by chlorine atom, hydrogen atom or by both; R
1Be the alkylidene group of carbonatoms 1～5 or the hydroxy alkylidene of carbonatoms 2～5; R
2Be the alkylidene group of carbonatoms 1～12, the oxyalkylene group of carbonatoms 2～50 or the hydroxy alkylidene of carbonatoms 3～15; R
3, R
4, R
5And R
6Can represent at least a in the fluoro-alkyl of the alkyl of carbonatoms 1～4 or carbonatoms 1～3 identical or differently; X is Sauerstoffatom, sulphur atom, NH or CO
2Y and Z are integers, and its total amount is 5～1000 integer; Y/Z is 0.5～200 scope; But Z is more than 2, R
1Or R
2In to have one at least be above-mentioned hydroxy alkylidene),
Said general formula (III) is:
(R
7)
aSiZ
4-a(III) (in the formula, R
7Be alkyl, fluoro-alkyl, alkenyl or phenyl; A is 0 or 1; Z be in halogen atom, alkoxyl group, acyloxy, ketoxime base, alkenyloxy, amino or the amide group more than a kind or 2 kinds).
5. the lubricant of making by claim 1 or 2 described fluosilicic oxyalkane compounds.
6. the fiber treatment agent of making by claim 1 or 2 described fluosilicic oxyalkane compounds.
7. the remover of making by claim 3 or 4 described solidified nature fluoro siloxane compositions.
8. the water and oil repellent agent of making by claim 3 or 4 described solidified nature fluoro siloxane compositions.
9. the didirtresistance of being made by claim 3 or 4 described solidified nature fluoro siloxane compositions applies agent.
10. the Abherent of being made by claim 3 or 4 described solidified nature fluoro siloxane compositions applies agent.
11. the optics usefulness of being made by claim 3 or 4 described solidified nature fluoro siloxane compositions applies agent.
12. the sealing agent of making by claim 3 or 4 described solidified nature fluoro siloxane compositions.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP117263/1994 | 1994-05-30 | ||
| JP117263/94 | 1994-05-30 | ||
| JP11726394 | 1994-05-30 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011012676A Division CN1169812C (en) | 1994-05-30 | 1995-05-25 | Fluosilicic oxyalkane compound and composition containing the same compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149304A true CN1149304A (en) | 1997-05-07 |
| CN1069665C CN1069665C (en) | 2001-08-15 |
Family
ID=14707437
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95193303A Expired - Lifetime CN1069665C (en) | 1994-05-30 | 1995-05-25 | Fluorosilicone compound and composition containing the same |
| CNB011012676A Expired - Lifetime CN1169812C (en) | 1994-05-30 | 1995-05-25 | Fluosilicic oxyalkane compound and composition containing the same compound |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011012676A Expired - Lifetime CN1169812C (en) | 1994-05-30 | 1995-05-25 | Fluosilicic oxyalkane compound and composition containing the same compound |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5734001A (en) |
| EP (1) | EP0803528A4 (en) |
| JP (1) | JP3520522B2 (en) |
| KR (1) | KR100266922B1 (en) |
| CN (2) | CN1069665C (en) |
| TW (1) | TW357166B (en) |
| WO (1) | WO1995033001A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339204C (en) * | 2003-05-23 | 2007-09-26 | 纳幕尔杜邦公司 | Mold release composition and process therewith |
| CN101224594B (en) * | 2007-12-18 | 2011-05-04 | 东莞市拓扑光电科技有限公司 | Nanometer wood protective agent and preparing method thereof |
| CN102558560A (en) * | 2011-09-21 | 2012-07-11 | 方舟(佛冈)化学材料有限公司 | Fluorosilicone oil and preparation method of fluorosilicone oil |
| CN103057222A (en) * | 2011-10-21 | 2013-04-24 | 新辉光电股份有限公司 | Backboard device of photovoltaic cell |
| CN105666752A (en) * | 2016-01-21 | 2016-06-15 | 衢州氟硅技术研究院 | Fluorosilicone release agent composite |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19606011B4 (en) * | 1996-02-17 | 2006-11-23 | Degussa Ag | Use of a preparation for producing an antifouling coating |
| JP3879657B2 (en) * | 2002-11-20 | 2007-02-14 | 日東電工株式会社 | Curable resin composition for antireflection layer, antireflection layer, antireflection film, optical element and image display device |
| JP2006265485A (en) * | 2005-03-25 | 2006-10-05 | Shin Etsu Chem Co Ltd | Room-temperature-curable organopolysiloxane composition |
| CN100396751C (en) * | 2005-06-21 | 2008-06-25 | 广州市白云化工实业有限公司 | Organic silicon fluoro water proofing agent and its preparation method |
| US20100235972A1 (en) * | 2005-07-28 | 2010-09-23 | Guasch Michael N | Fuel repellent compositions, fabrics and articles |
| JP5262255B2 (en) * | 2008-04-09 | 2013-08-14 | Ｄｉｃ株式会社 | Fluorine-containing acrylate and UV-curable composition |
| US8038770B2 (en) * | 2008-12-01 | 2011-10-18 | Eaton Corporation | Separator for degassing fluid |
| JP5083342B2 (en) * | 2010-02-25 | 2012-11-28 | トヨタ自動車株式会社 | STRUCTURAL MEMBER FOR INTERNAL COMBUSTION ENGINE AND METHOD FOR FORMING WATER AND OIL REPELLANT COATING |
| CN102260400B (en) * | 2010-05-27 | 2013-06-05 | 上海欣影电力科技发展有限公司 | Acrylic acid modified fluorosilicone polymer, and preparation method thereof |
| WO2013172177A1 (en) * | 2012-05-18 | 2013-11-21 | ダイキン工業株式会社 | Fluoropolyether-group-containing silicone compound |
| KR101669338B1 (en) * | 2014-11-26 | 2016-10-26 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
| CN112724829B (en) * | 2020-12-28 | 2022-04-19 | 苏州德达材料科技有限公司 | Anti-fingerprint material and preparation method and application thereof |
| CN114683447B (en) * | 2022-03-09 | 2023-09-05 | 海南汉地阳光石油化工有限公司 | Release agent for rubber processing and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS548640A (en) * | 1977-06-22 | 1979-01-23 | Mitsubishi Gas Chem Co Inc | Coating for treating the surface of plastic molded product |
| DE3722375A1 (en) * | 1987-07-07 | 1989-01-19 | Hoechst Ag | URETHANES CONTAINING FLUOR AND POLYSILOXANE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| US5124467A (en) * | 1990-07-20 | 1992-06-23 | Ciba-Geigy Corporation | Perfluoroalkypolyoxyalkylpolysiloxane surfactants |
| JPH07119364B2 (en) * | 1990-08-03 | 1995-12-20 | 信越化学工業株式会社 | Curable silicone composition and cured product thereof |
| TW203094B (en) * | 1992-01-21 | 1993-04-01 | Gen Electric | |
| US5548054A (en) * | 1992-03-10 | 1996-08-20 | Kao Corporation | Fluorine-modified silicone derivative, production thereof and cosmetic containing the same |
| JP2720127B2 (en) * | 1992-03-10 | 1998-02-25 | 花王株式会社 | Fluorine-modified silicone, process for producing the same, and cosmetic containing the same |
-
1995
- 1995-05-25 EP EP95919639A patent/EP0803528A4/en not_active Ceased
- 1995-05-25 CN CN95193303A patent/CN1069665C/en not_active Expired - Lifetime
- 1995-05-25 WO PCT/JP1995/001008 patent/WO1995033001A1/en not_active Application Discontinuation
- 1995-05-25 KR KR1019960706390A patent/KR100266922B1/en not_active IP Right Cessation
- 1995-05-25 US US08/737,498 patent/US5734001A/en not_active Expired - Lifetime
- 1995-05-25 CN CNB011012676A patent/CN1169812C/en not_active Expired - Lifetime
- 1995-05-25 JP JP50064796A patent/JP3520522B2/en not_active Expired - Fee Related
- 1995-07-28 TW TW084107954A patent/TW357166B/en active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339204C (en) * | 2003-05-23 | 2007-09-26 | 纳幕尔杜邦公司 | Mold release composition and process therewith |
| CN101224594B (en) * | 2007-12-18 | 2011-05-04 | 东莞市拓扑光电科技有限公司 | Nanometer wood protective agent and preparing method thereof |
| CN102558560A (en) * | 2011-09-21 | 2012-07-11 | 方舟(佛冈)化学材料有限公司 | Fluorosilicone oil and preparation method of fluorosilicone oil |
| CN103057222A (en) * | 2011-10-21 | 2013-04-24 | 新辉光电股份有限公司 | Backboard device of photovoltaic cell |
| CN105666752A (en) * | 2016-01-21 | 2016-06-15 | 衢州氟硅技术研究院 | Fluorosilicone release agent composite |
| CN105666752B (en) * | 2016-01-21 | 2019-05-14 | 衢州氟硅技术研究院 | A kind of fluorine silicon mold release agent composition altogether |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995033001A1 (en) | 1995-12-07 |
| TW357166B (en) | 1999-05-01 |
| CN1335319A (en) | 2002-02-13 |
| EP0803528A1 (en) | 1997-10-29 |
| CN1169812C (en) | 2004-10-06 |
| CN1069665C (en) | 2001-08-15 |
| US5734001A (en) | 1998-03-31 |
| KR100266922B1 (en) | 2000-09-15 |
| EP0803528A4 (en) | 1998-01-07 |
| JP3520522B2 (en) | 2004-04-19 |
| KR970702890A (en) | 1997-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1069665C (en) | Fluorosilicone compound and composition containing the same | |
| CN1196757C (en) | Scratch-resistant coating | |
| CN1246364C (en) | Organosilicon compounds having polyoxyalkylene radicals | |
| CN1073137C (en) | Curable resin composition for water-based paints | |
| CN100349732C (en) | Thermally stable, moisture curable polysilazanes and polysiloxazanes | |
| CN1194034C (en) | Rubber composition intended for manufacture of articles with elastomeric base containing oxygenated functions and silica as filler | |
| CN1168768C (en) | Rubber compositions | |
| CN1113509A (en) | Coating composition capable of yielding a cured product having a high refractive index and coated articles obtained therefrom | |
| CN1916002A (en) | Organosilicon compounds and their preparation and their use | |
| CN1169690A (en) | Release agent, hardened skin-film obtained from said release agent and forming method using said release agent | |
| CN1271122C (en) | Silicone compsn. which can be crosslinked into elastomer by hydrosilylation in presence of carbene-based metal catalysts, and catalysts of this type | |
| CN1129227A (en) | Single package ambient curing polymers | |
| CN1807434A (en) | Mercapto silane | |
| CN1051982C (en) | A glazing material comprising a high-hard transparent resin | |
| CN1107864A (en) | Aqueous dispersions of organopoly-siloxanes | |
| CN1092691C (en) | Aqueous dispersions of organopolysiloxanes | |
| CN1612918A (en) | Silicone composition crosslinkable into elastomer by hydrosilylation, in the presence of carbene-based metal catalysts, and catalysts | |
| CN1882618A (en) | Fluorine containing photocurable composition | |
| CN101080317A (en) | Composite material, coating fluid and method for producing composite material | |
| CN1829762A (en) | Silicon-containing polymer, process for rpoducing the same, heat-resistant resin composition, and heat-resistant film | |
| CN1238388C (en) | Fluorine contained multipolymer and coating composition | |
| CN87107861A (en) | Curing composition | |
| CN1293682A (en) | Novel polyisocyanate and process for producing the same | |
| CN1955238A (en) | Oligomer diacetyl acetate alkylene diester metal chelate coating drier and preparation and application | |
| CN1742048A (en) | Anti-fouling varnish, method for application of said varnish to a silicone support and support treated thus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20150525 Granted publication date: 20010815 |